EP1446512B1 - Martensitic stainless steel and method for manufacturing same - Google Patents

Martensitic stainless steel and method for manufacturing same Download PDF

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Publication number
EP1446512B1
EP1446512B1 EP02801999A EP02801999A EP1446512B1 EP 1446512 B1 EP1446512 B1 EP 1446512B1 EP 02801999 A EP02801999 A EP 02801999A EP 02801999 A EP02801999 A EP 02801999A EP 1446512 B1 EP1446512 B1 EP 1446512B1
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Prior art keywords
steel
stainless steel
martensitic stainless
retained austenite
austenite
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French (fr)
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EP1446512A1 (en
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Mitsuru Sumitomo Metal Industries Ltd. YOSHIZAWA
Kunio c/o Sumitomo Metal Industries Ltd. KONDO
Masaaki Sumitomo Metal Industries Ltd. IGARASHI
Yuichi c/o Sumitomo Metal Industries Ltd. KOMIZO
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Nippon Steel Corp
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Sumitomo Metal Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/84—Controlled slow cooling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite

Definitions

  • the present invention relates to a martensitic stainless steel, which has excellent properties as for the corrosion resistance, the stress corrosion cracking resistance, the mechanical strength and the toughness, thereby preferably usable as a material for a steel pipe to construct, e.g., an oil well or a gas well (hereinafter generally being referred to as "oil well") as well as to transport crude oil or natural gas.
  • the present invention also relates to a method for manufacturing such a martensitic stainless steel.
  • API-13% Cr steel (13% Cr - 0.2% C), which is specified according to the standard of the API (American Petroleum Institute), is widely used in such an environment, because it has an excellent corrosion resistance to carbon dioxide.
  • the API-13% Cr steel can be used as a material for a conventional oil country tubular goods which require a mechanical strength of order of yield stress 552 - 655 MPa (80 - 95 ksi).
  • API-13% Cr steel has a relatively small toughness and therefore cannot be used as a material for a deep oil well steel pipe which requires a much greater mechanical strength of order of yield stress more than 759 MPa (110 ksi).
  • improved type 13% Cr steel which includes carbon in an extremely reduced amount and which includes Ni instead of carbon, has been developed to improve the corrosion resistance. Since the improved type 13% Cr steel provides an excellent toughness even in an increased mechanical strength and therefore can be used in a much severer corrosive environment, it is increasingly used in an environment requiring a high mechanical strength. However, a decrease in the C content tends to provide the precipitation of ⁇ ferrite, which are harmful for the hot workability, the corrosion resistance, the toughness and the like as for steel. As a result, an appropriate amount of Ni, which is considerably expensive, has to be included in the steel in accordance with the amounts of both Cr and Mo added, thereby causing its price to be considerably increased.
  • the invention has been completed on the basis of the findings, and the object is attained by (1) the following martensitic stainless steels and (2) the following method of producing such a martensitic stainless steel:
  • a martensitic stainless steel consisting of carbon in a content of 0.01 - 0.1 mass %, chromium in a content of 9 - 15 mass %, and optionally Si: 0.05 - 1%, Mn: 0.05 - 1.5%, P: not more than 0.03%, S: not more than 0.01 %, Ni: 0.1 - 7%, Al: not more than 0.05% and N: not more than 0.1 %, and further optionally one or more elements selected from Cu: 0.04 - 4%, Mo: 0.05 - 3%, Ti: 0.005 - 0.5%, V: 0.005 - 0.5%, Nb: 0.005 - 0.5%, B: 0.0002 - 0.005%, Ca: 0.0003 - 0.005%, Mg: 0.0003 - 0.005% and rare earth elements: 0.0003 - 0.005% in mass %, the residual being Fe and impurities, wherein the thickness of retained austenite in the steel is smaller than 100 nm, and
  • a martensitic stainless steel according to the invention preferably includes Si: 0.05 - 1 %, Mn: 0.05 - 1.5%, P: not more than 0.03%, S: not more than 0.01 %, Ni: 0.1 - 7%, Al: not more than 0.05% and N: not more than 0.1 % in mass %, the residual being Fe and impurities.
  • a martensitic stainless steel according to the invention preferably includes one or more elements in the following compositions or each of the following groups in addition to the above-mentioned martensitic stainless steel:
  • a method for producing a martensitic stainless steel wherein one of the above-mentioned martensitic stainless steels is heated at a temperature of the Ac 3 point or more, and then cooled from 800°C to 400°C a cooling rate of not less than 0.08°C/sec, and further cooled down to 150°C at a cooling rate of not more than 1°C/sec.
  • the above-mentioned cooling rate is referred to the condition specified in the final stage of heat treatment.
  • the cooling rate can also be employed such that, after a steel is heated at a temperature of the Ac 3 point or more and hot-worked, the steel is cooled from 800°C to 400°C at a cooling rate of not less than 0.08°C/sec, and further cooled down to 150°C at a cooling rate of not more than 1°C/sec.
  • the present invention is realized on the basis of the findings, which is accumulated by the following investigations. These investigations and the approach applied thereto are as follows:
  • the conventional heat treatment i.e., the heating in a dual phase region at a temperature of Ac 1 - Ac 3 , was carried out by changing the temperature and the heating duration, and then the shape and amount of the precipitated retained austenite particles as well as the mechanical properties were studied.
  • Fig. 1 shows an electron microscopic photograph of a metal structure which was obtained by heating 12% Cr-6.2% Ni-2.5% Mo-0.007%C steel in dual phase region (640°C, for 1 hr, and natural cooling).
  • the retained austenite is precipitated in the form of relatively coarse grains inside the parent phase of martensite and in the vicinity of the old austenite grain boundaries.
  • the thickness of a retained austenite particle was approximately 150 nm and the yield stress obtained was as small as 607 MPa.
  • the formation of relatively coarse retained austenite particles is due to the fact that the heating in a dual phase region at a temperature of Ac 1 - Ac 3 provides relatively coarse precipitated particles of reverse transformed austenite in which elements for forming austenite, such as C, N, Ni, Cu, Mn and the like are enriched.
  • the temperature (the Ms point) at which the martensitic transformation of austenite portions starts and the temperature (the Mf point) at which the martensitic transformation is completed greatly decrease, so that some of the reverse transformed austenite particles remain in the form of relatively coarse particles when it is cooled down at room temperature.
  • the process in which coarse retained austenite particles are formed is characterized in that, when a steel is held for a time interval in a dual phase region (high temperature) in which atoms are active in diffusion, the content of an element diffused into the reverse transformed austenite increases, thereby causing both Ms and Mf points to be markedly decreased. As a result, the retained austenite particles formed in the steel become relatively coarse. Such coarse austenite particles may improve the toughness, but at the same time causes the mechanical strength to be decreased, thereby making it difficult to simultaneously obtain a high mechanical strength and a high toughness by applying the method for precipitating the retained austenite particles on the basis of the heating in a dual phase region.
  • the retained austenite can be precipitated in the form of a fine particle not by heating a 12% Cr - 6.2% Ni - 2.5% Mo - 0.007% C steel similar to the above in a dual phase region, but by spontaneously cooling the steel. It was found that no retained austenite particles were precipitated, even if the cooling rate was varied, and that the toughness was relatively low, although a high mechanical strength was obtained.
  • Fig. 2 shows one of electron microscopic photographs of a metal structure which was obtained by the following procedures that a 11% Cr-0.5%Ni-0.25% Mo-0.03% C steel was first heated at a temperature of Ac 3 point or more, and cooled from 800°C to 400°C in an average cooling rate of 0.8°C/sec, and finally cooled from 400°C to 150°C at an average cooling rate of 0.13°C/sec.
  • the lath interface means an interface, which is newly formed by the martensitic transformation, and it includes an interface of packet and/or block, which is an interface between laths having different orientations.
  • the chemical composition, the metal structure and the manufacturing method are specified as above. The reason for such specification will be described. Firstly, the chemical composition of the martensitic stainless steel according to the invention will be described. In the following description, the chemical composition is expressed by mass %.
  • Carbon is an element for forming austenite, and provides an effect that the austenite is enriched and stabilized in the course of cooling, thereby remaining non-transformed.
  • carbon concentrates in the non-transformed austenite regions on the martensite lath interfaces, thereby causing the austenite to be stabilized.
  • a carbon content of not less than 0.01% is required.
  • a carbon content of more than 0.1% provides a prominent increase in the mechanical strength of the steel, but also provides a marked decrease in the toughness. Moreover, chromium carbide tends to precipitate in grain boundaries, thereby causing the corrosion resistance and the stress corrosion crack resistance in a corrosive environment containing CO 2 , H 2 S or the like to be deteriorated.
  • a usable range of carbon content should be determined so as to be 0.01- 0.1 %. In this case, the C content should be preferably greater than 0.02%, more preferably 0.02 - 0.08%, and further more preferably 0.02 - 0.045%.
  • Chromium is an element indispensable for obtaining the corrosion resistance of a stainless steel.
  • this element is important for obtaining both the corrosion resistance and the stress corrosion crack resistance in a corrosive environment.
  • a chromium content of not less than 9% practically provides a available reduction in the corrosion rate under various conditions.
  • a chromium content more than 15% tends to form ⁇ ferrite in the metal structure, thereby causing the mechanical strength to be decreased and further the hot workability and the toughness to be deteriorated.
  • a usable range of Cr content should be determined so as to be 9 - 15%. In this case, a preferable range should be less than 9 - 12%.
  • the steel according to the invention pertains to a conventional martensitic stainless steel.
  • the martensitic stainless steel according to the invention preferably includes Si, Mn, P, S, Ni, Al and N in the following ranges of content, the residual being Fe and impurities.
  • Silicon is an element serving as a deoxidizer. However, a silicon content less than 0.05% provides an incomplete effect of deoxidization. On the other hand, a silicon content more than 1% reduces the toughness. Accordingly, the preferable Si content should range from 0.05% to 1%
  • Manganese is an element effective for increasing the mechanical strength of the steel material, and for forming austenite to suppress the precipitation of ⁇ ferrite in the treatment of quenching a steel material, thereby causing the metal structure in the steel material to be stabilized and martensite to be formed.
  • a Mn content of less than 0.05% provides a reduced effect for forming the maretensite.
  • a Mn content of more than 1.5% deteriorates both the toughness and the corrosion resistance. Accordingly, a preferable Mn content should range from 0.05% to 1.5%.
  • Phosphor is normally included as an impurity in steel and has an extremely harmful influence on the toughness of the steel, along with the deterioration of the corrosion resistance in a corrosive environment containing CO 2 and the like. As a result, it is preferable that the P content should be as small as possible. However, there is no problem so long as the content is retained within 0.03%. Hence, the upper limit of the P content should be determined so as to be 0.03%.
  • Sulfur is included as an impurity in steel, similarly to P, and has an extremely harmful influence on the hot workability of the steel.
  • the S content should be as small as possible.
  • the upper limit of the S content should be determined so as to be 0.01%.
  • Nickel is an element effective for forming austenite and suppresses the precipitation of ⁇ ferrites in the treatment of quenching a steel material, thereby causing the metal structure in the steel material to be stabilized and martensite to be formed.
  • Ni is included in a content not less than 0.1%.
  • a Ni content of more than 7% provides an increase in the price of the steel material as well as in the amount of retained austenite, thereby making it impossible to obtain a desired mechanical strength.
  • the Ni content should be set to be preferably 0.1 - 7%, more preferably 0.1 - 3.0%, and further more preferably 0.1 - 2.0%.
  • Aluminum should not always be included in steel.
  • A1 is an element effective as a deoxidizer.
  • Al When, therefore, Al is used as a deoxidizer, it may be included in a content of not less than 0.0005%.
  • an Al content more than 0.05% deteriorates the toughness of the steel.
  • the Al content should be set to be not more than 0.05%.
  • N Nitrogen should not always be included in steel, since it deteriorates the toughness.
  • N is an element suppressing the precipitation of ⁇ ferrites in the treatment of quenching a steel material, thereby causing the metal structure in the steel material to be stabilized and martensite to be formed. Accordingly, it may be included at need.
  • An N content more than 0.1% markedly deteriorates the toughness and is apt to generate welding cracks in the welding process of steel material. As a result, the N content should be set to be not more than 0.1%.
  • Copper should not always be included.
  • Cu serves to enhance the corrosion resistance and stress corrosion cracking resistance in a corrosive environment containing CO 2 , Cl, and H 2 S. Such an effect can be obtained with a Cu content not less than 0.05%.
  • a Cu content more than 4% provides saturation in the effect and further reduces the hot workability and the toughness. Accordingly, it is preferable that the Cu content should be set to be 0.05 - 4% in case of wishing to include.
  • Molybdenum should not always be included.
  • Mo serves to enhance the corrosion resistance and stress corrosion cracking resistance in a corrosive environment containing CO 2 , Cl - , and H 2 S. Such an effect can be obtained with a Mo content not less than 0.05%.
  • a molybdenum content more than 3% saturates such effect and further reduces both the hot workability and the toughness. Accordingly, it is preferable that the Mo content should be 0.05 - 3%, if necessary.
  • each of these elements should not always be included. However, each element enhances the stress corrosion cracking resistance in a corrosive environment of H 2 S. This effect can be obtained by adding one or more of these elements to the steel.
  • a content of not less than 0.005% provides a prominent effect as for any one of Titanium, Vanadium and Niobium. However, a content more than 0.5% deteriorates the toughness of the steel. Accordingly, the content should be set to be 0.005 - 0.5% for anyone of Titanium, Vanadium and Niobium, when wishing to add.
  • Each of these elements enhances the hot workability of steel. Therefore, when wishing to improve, in particular, the hot workability, it is preferable that one or more of these elements are added. Such a prominent effect can be obtained either at a content not less than 0.0002% in the case of Boron, or at a content not less than 0.0003% in the case of Calcium, Magnesium or rare earth elements. However, a content more than 0.005% for all the elements reduces the toughness and also deteriorates the corrosion resistance in a corrosive environment containing CO 2 and the like. Accordingly, the content should be set to be 0.0002 - 0.005% for Boron and 0.0003 - 0.005% for Calcium, Magnecium or rare earth elements.
  • the martensitic stainless steel according to the invention includes the following retained austenite in the parent phase of martensite structure:
  • the retained austenite form sites in the present invention mainly attribute to the lath interfaces in the martensite.
  • the thickness of the retained austenite is specified as follows: Retained austenite in a thin film of a steel material was taken in a dark field image by an electron microscope and then the minor axis thereof was measured. In the quantitative determination, each retained austenite was regarded as an approximate ellipse and then the minor axis thereof was determined by the image analysis method. Ten fields having an area of 1,750 nm ⁇ 2,250 nm were selected at random from each specimen, and the minor axis was measured for all of the retained austenite particles in each field. Thereafter, the thickness of the austenite was determined as an average value from the measured minor axes.
  • 111 ⁇ /(111 ⁇ + 110 ⁇ ) is a quantity which is determined in proportion to the amount of the retained austenite.
  • this quantity is smaller than 0.005
  • the amount of the retained austenite is too small to improve the toughness.
  • this quantity is more than 0.05, the amount of the retained austenite is too large to attain a high mechanical strength.
  • the X-ray diffraction intensity was measured at a scan speed of 0.2 degrees/min for the surface of respective samples, after removing the work-damaged layer by the chemical etching method.
  • the integral intensities of 111 ⁇ and 110 ⁇ were determined, using JADE(4.0) for Microsoft® Windows® by Rigaku Corp., after the background treatment and peak dispersion treatment were carried out.
  • a steel material is heated at a temperature of the Ac 3 point or more to form a thick steel plate, steel pipe or the like with a hot working. Thereafter, the good thus formed is cooled from 800°C to 400°C at a cooling rate of not less than 0.08°C/sec and then cooled down to 150°C at a cooling rate of not more than 1°C/sec.
  • the steel material is heated at a temperature of the Ac 3 point or more as a final heat treatment. Thereafter, the material is cooled from 800°C to 400°C at a cooling rate of not less than 0.08°C/sec and then cooled down to 150°C at a cooling rate of not more than 1°C/sec.
  • the temperature of the Ac 3 point in the present invention is different from chemical component to chemical component, but it is generally about 750 - 850°C.
  • the reason why the cooling rate of not less than 0.08°C/sec should be employed in the temperature range of 800°C - 400°C is due to the fact that, although the steel material has a very good quenching property, the employment of a cooling rate of less than 0.08°C/sec results in the precipitation of coarse carbides and therefore no sufficient enrichment of carbon can be obtained, even if a slow cooling is applied in the temperature range from 400°C to 150°C, so that no sufficient amount of retained austenite can be obtained, thereby causing the toughness to be reduced.
  • carbon is enriched in regions of non-transformed austenite between martensite laths below a temperature of the Ms point and the austenite remains in the lath interfaces by stabilizing the austenite.
  • a cooling rate of greater than 1°C/sec is employed in the cooling from 400°C to 150°C, the martensitic transformation is completed before carbon is concentrated inside the austenite, so that no sufficient amount of retained austenite can be obtained, thereby causing the toughness to be deteriorated.
  • both the martensitic stainless steel and the manufacturing method thereof intend not to obtain a desirable metal structure by specifying the chemical component of the steel, but to obtain an excellent property regarding the mechanical strength and the toughness from a favorable metal structure by utilizing a steel material having a specified chemical component as well as by employing a suitable manufacturing method.
  • the block thus formed was heated up to 1200°C and then hot rolled to form six kinds of steel plates having a thickness of 7 mm, 15 mm, 20 mm, 25 mm, 35 mm and 45 mm, respectively. Thereafter, these steel plates were cooled at various cooling rates both in a high temperature range from 800°C to 400°C and in a low temperature range from 400°C to 150°C. As for part of these steels, the re-heating was further carried out after cooled down to room temperature, and then the steels were again cooled under the same cooling conditions as above.
  • the steels indicated by marks 12, 27 and 28 were further tempered.
  • the rolling finish temperature, the conditions of re-heating, the cooling rates and the tempering conditions are listed in Table 2.
  • the properties of the steel plates thus produced were investigated as for the tensile property (yield stress: YS(MPa)), the impact property (fracture appearance transition temperature: vTrs (°C)) and the distribution of retained austenite particles.
  • the tensile test was made for each rod having a diameter of 4 mm, which was machined from the corresponding steel plate after the heat treatment.
  • the Charpy impact test was made as for a 5 mmx10mmx55mm subsized block which was machined similarly from the corresponding steel plate after the heat treatment, using a 2 mm V notch test piece.
  • the thickness of the retained austenite was determined from the minor axis of the approximate ellipse in a dark field image of a thin film prepared from the steel material, employing an electron microscope, as described above.
  • the shape of retained austenite particles was approximated to an ellipse and the minor axis of the ellipse was determined by means of an image analysis method. In this case, 10 image fields having an area of 1,750 nm ⁇ 2,250 nm were selected at random from each specimen. All of the retained austenite particles were observed in the respective image fields, and the thickness of the austenite was determined by the average value of the minor axes thus determined.
  • the steel materials, in which the thickness of the retained austenite is not more than 100 nm, are indicated by a symbol ⁇ .
  • the amount of the retained austenite particles was determined for the respective specimens, using the X-ray diffraction method.
  • each steel material was cut to form a block having a 2 mm thickness and a 20 mm width and a 20 mm length, and then the work-damaged layer was removed by using the chemical etching method.
  • the integral intensities of 111 ⁇ and 110 ⁇ were measured at a scanning speed of 0.2 degree/min after the background treatment and peak separation treatment, employing JADE (4.0) for Microsoft® Windows® by Rigaku Corp., the value of 111 ⁇ /(111 ⁇ + 110 ⁇ ) was determined.
  • Mark 13 indicates a result for a steel material including Cr content greater than the upper limit.
  • the morphology of the retained austenite (thickness and number thereof) satisfied the conditions specified by the invention, but a greater number of ⁇ ferrites were precipitated so that a desired mechanical strength could not be obtained.
  • Marks 14 and 15 indicate the results for steel materials including carbon content outside the specified range.
  • the steel material of mark 14 pertained to a steel including extremely low content of carbon.
  • the steel material provided a low mechanical strength and includes retained austenite, even if it was slowly cooled in the temperature range from 400°C to 150°C. As a result, high toughness could not be obtained.
  • the steel material of mark 15 had a C content greater than the upper limit. The retained austenite particles having a desired shape were obtained and the mechanical strength was extremely enhanced. Nevertheless the toughness decreased.
  • Marks 16 to 26 indicate the results either for the steel materials that were prepared under the condition specified by the invention but did not provide retained austenite particles having a desired shape, or for the steel material that provided retained austenite particles having a desired shape but a very reduced number thereof.
  • the steel materials of marks 17 and 22 were slowly cooled in the high temperature range of 800 - 400°C, thereby causing the carbides to be precipitated. Accordingly, carbon could not be sufficiently enriched and therefore retained austenite particles could not be obtained, thereby causing the toughness to be deteriorated.
  • the steel materials of marks 16, 18 to 21 and 23 to 26 were quenched in the high temperature range of 800 - 400°C in the cooling stage after rolling finished or after the re-heating, so that no carbides were generated and solved carbon could be obtained.
  • the enrichment of carbon was suppressed by the quenching in the low temperature range of 400 - 150°C, thereby making it difficult to generate the retained austenite. As a result, the toughness was deteriorated, although a high mechanical strength could be obtained.
  • the treatment of precipitating the retained austenite was applied, and further the tempering was made in the region of dual phase, i.e., ferrite/austenite phase.
  • the precipitation of retained austenite greatly improved the toughness.
  • the thickness of the retained austenite did not satisfy the range specified by the invention, thereby making it impossible to obtain a high mechanical strength.
  • Marks 1 to 11 indicate embodiments, in which, using a steel material specified by the invention, in a cooling stage after the completion of rolling or after the re-heating followed by the cooling down to room temperature, the steel material was cooled from 800°C to 400°C at a cooling rate not less than 0.08°C/sec to suppress the precipitation of carbides, and further slowly or mildly cooled in the low temperature range of 400 - 150°C to form fine retained austenite particles, so that the metal structure specified by the invention was obtained. It is found that all the steel materials in the inventive example provided a high mechanical strength and a remarkably improved toughness, compared with those in the comparative example.
  • the metal structure is further specified. Accordingly, the desired or aimed properties or performance of the stainless steel can also be obtained, if such a metal structure is obtained by utilizing the manufacturing method other than that specified by the invention.
  • the quenching was made in the low temperature range of 400 - 150°C and then the tempering was made for very short time using an induction furnace to form fine retained austenite particles.
  • This procedure pertains to the category of the so-called tempering process in a dual phase region. In this case, a high mechanical strength and a high toughness could be obtained.
  • the control of morphology in the retained austenite phase as specified by the present invention provides a high mechanical strength as well as a high toughness.
  • the martensitic stainless steel according to the present invention includes C: 0.01 - 0.1% and Cr: 9 - 15%, and retained austenite phase in the steel having a thickness of not more than 100 nm so that the X-ray integral intensities of 111 ⁇ and 110 ⁇ satisfy the following formura: 0.005 ⁇ 111 ⁇ ⁇ / 111 ⁇ ⁇ + 110 ⁇ ⁇ ⁇ 0.05
  • the martensitic stainless steel having such a chemical composition and such a structure has a relatively high content of carbon, thereby enabling a higher mechanical strength and a greater toughness to be obtained, together with an excellent corrosion resistance. Therefore, it is particularly effective to use the martensitic stainless steel according to the invention as a material for constructing a deep oil well. Moreover, there is no need to reduce the carbon content, as done in the conventional improved 13% Cr steel. In conjunction this, a decrease in the content of expensive Ni makes it possible to reduce the manufacturing cost.

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
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EP02801999A 2001-10-19 2002-10-04 Martensitic stainless steel and method for manufacturing same Expired - Lifetime EP1446512B1 (en)

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JP2001322548A JP2003129190A (ja) 2001-10-19 2001-10-19 マルテンサイト系ステンレス鋼およびその製造方法
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PCT/JP2002/010394 WO2003035921A1 (en) 2001-10-19 2002-10-04 Martensitic stainless steel and method for manufacturing same

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CN1571859A (zh) 2005-01-26
EP1446512A1 (en) 2004-08-18
ATE397677T1 (de) 2008-06-15
CA2463783C (en) 2008-04-15
US20030217789A1 (en) 2003-11-27
BR0213414A (pt) 2004-11-03
DE60226997D1 (de) 2008-07-17
US7662244B2 (en) 2010-02-16
MXPA04003690A (es) 2004-07-30
WO2003035921A1 (en) 2003-05-01
NO341414B1 (no) 2017-10-30
CA2463783A1 (en) 2003-05-01
BR0213414B1 (pt) 2011-01-11
AR036880A1 (es) 2004-10-13
JP2003129190A (ja) 2003-05-08
NO20041574L (no) 2004-05-28

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